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I ask because I help out with the running of http://forums.gameplay.com/ - possibly the largest vBulletin powered forum in the world at 1.6 million posts. We are having serious performance problems at peak access times and any tips on improving performance would be welcome

The best source of information is the Server Configuration forum at vBulletin.com and the MySQL documentation.

With that many posts though you may want to contact Matt Rogish (I think that is correct) at Fanhome.com. He has ported vBulletin to Sybase. Sybase would be better able to handle that kind of load. There is a free older version available for Redhat Linux.